Abstract

We use density functional theory to predict and evaluate 10 novel covalent organic frameworks (COFs), labeled (X4Y)(BDC)3, (X = C/Si; Y = C, Si, Ge, Sn, and Pb), with topology based on metal organic framework isoreticular metal-organic framework (IRMOF-1), but with new elements substituted for the corner atoms. We show that these new materials are stable structures using frequency calculations. For two structures, (C4C and Si4C) molecular dynamics simulations were performed to demonstrate stability of the systems up to 600 K for 10 ps. This demonstrates the remarkable stability of these systems, some of which may be experimentally accessible. For the C4C material, we also explored the stability of isolated corners and linkers and vacuum and started to build the structure from these pieces. We discuss the equilibrium lattice parameters, formation enthalpies, electronic structures,chemical bonding, and mechanical and optical properties. The predicted bulk moduli of these COFs range from 18.9 to 23.9 GPa, larger than that of IRMOF-1 (ca. 15.4 GPa), and larger than many existing 3D COF materials. The band gaps range from 1.5 to 2.1 eV, corresponding to 600–830 nm wavelength (orange through near infrared). The negative values of the formation enthalpy suggest that they are stable and should be experimentally accessible under suitable conditions. Seven materials distort the crystal structure to a lower space group symmetry Fm-3, while three materials maintain the original Fm-3m space group symmetry. All of the new materials are highly luminescent. We hope that this work will inspire efforts for experimental synthesis of these new materials.

Support in Germany by Fellowship of Hanse-Wissenschafts-Kolleg (HWK) and Research Scholarship of University of Bremen (to L.-M.Y.) is gratefully acknowledged. We thank the Minnesota supercomputer Institute, HLRN & JULICH supercomputers for support. Dedicated to Professor Dong-Yuan Zhao on the occasion of his birthday.